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By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of-the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication.1-5 In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators. of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating and distillation in-the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char.6 Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking. qualities by inspection of chemical analyses of coals.7 A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: Coking index =[ a+b+c+d 5] a equals 22/oxygen content on ash and moisture- free basis, . b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/1.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above 1.1 indicate good coking tendencies. Although generally usable, this formula is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct.8,9 Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1952

By O. D. Gaither

This paper is an analytical study of the flow of fluids through small vertical conduits. Small conduits are defined as 11/4-in. nominal diameter tubing size and smaller, and approximately twice this area for annular conduits (i.e., 1- X 21/2-in. annulus and smaller). Experimental data are presented for the 1-X2-in. and 11/4- X 2%-in. annuli, and the I-in. and 11/4-in. tubing, since these represent the small conduit sizes and configurations generally encountered in oilfield applications. Data have been gathered for these conduits for single-phase water, single-phase gas and two-phase water-gas mixtures, with particular emphasis on high gas-liquid ratios. Water rates in excess of 2,000 BID and gas rates in excess of 2.5 MMcf/D, and two-phase flow ratios in between these two, represent the scope of the data gathered. Existing equations have been applied to predict flowing pressures and compared with experimental data. New correlations have been developed. INTRODUCTION The increased economic pressure on the domestic oil industry in the United States has constantly required the use of new techniques and equipment designed to reduce the cost of finding and producing oil and gas. Since tangible items are most readily apparent in economic analysis, the advent of lower-cost well completions was inevitable. One of the methods used to reduce costs which has received widespread attention is the slim-hole completion technique where tubing is used as the well casing and in which small conduits are used for tubing if necessary. Small conduits, defined by Kirkpatrick1 as "11/4-in. diameter nominal tubing and smaller for tubing flow and less than twice the 11/4-in. diameter nominal tubing internal flow area for annulus flow", have also found widespread usage as siphon strings for de-watering gas wells and as "kill" strings in deep high-pressure oil and gas wells. The growing use of small-diameter tubing has resulted in an increased need for development of improved methods to measure or predict flowing bottom-hole pressures since the physical dimensions generally preclude the use of subsurface-recording pressure gauges. Even in the cases where small bombs are available, the relatively high velocities encountered at nominal flow rates make it necessary to use excessive weight bars or special hold-down devices. Attempts to use recognized correlations to accurately predict flowing or gas-lift performance in wells equipped with small conduits have been generally unsuccessful. Insufficient field data were available to allow the development of a correlation on this basis, and an experimental approach was applied in an attempt to obtain a workable relation. The experimental approach used to obtain the data presented in this paper was actually a compromise between a field installation and a laboratory study. A test well 1,000 ft in length was used to obtain flow data on single-phase liquid, single-phase gas and two-phase water-gas flowing mixtures. Liquid rates up to 2,200 B/D and gas rates up to 3 MMcf/D were used in the single-phase flow studies. Two-phase flow rates from 100 to 600 B/D with gas-liquid ratios from 500 to 8,000 cu ft/bbl were recorded. Experimental data were obtained for single- and two-phase flow through 1-in and 11/4-in. nominal tubing, and through the annuli between 1- and 2-in. and 11/4- and 2%-in. nominal tubing strings. Experimental results for the two-phase flow are compared to the Poettmann-Carpenter correlation2 which is widely used as a comparative standard for development of multiphase flow predictions in flowing and gas-lift wells. Correlations developed by Tek,3 Baxendell and Thomas" were also investigated. The experimental data recorded herein fell in between the two flow regimes as defined by Ros," and this correlation also failed to yield satisfactory results. The fact that existing correlations failed to confirm the experimental data led to the need for development of a new correlation. Although a two-phase flow study was the primary objective of this investigation, data were also recorded for single-phase flow of water and gas, and constants were developed relating to pipe roughness and equivalent diameters for annular flow. These single-phase studies assisted materially in the development of certain of the two-phase flow results. Considerable previous work has been published which presented relationship of surface measurements to bottom-hole condition. The works of Buthod and Whiteley,6 Jones,' Poettmannb and the Texas Railroad Commission" are classic examples of the successful use of mathematical relationships which allow acceptable predictions of subsurface pressures, when gas is the flowing fluid. Darcy and others have derived relationships which may be used with minor modifications to predict subsurface flowing conditions in injection and water-supply wells. As previously stated, the application of the single-phase flow relationships

By M. T. Simnad, G. Derge, I. George

Measurements of current efficiency on iron-silicate slags in iron crucibles showed that conduction is about 10 pct ionic in slags with less than 10 pct silica and about 90 pct ionic in slags with more than 34 pct silica, increasing linearly in the intermediate range. The balance of the conduction is electronic in character. Silicate ions are discharged at the anode with the evolution of gaseous oxygen. Transport experiments show that the ionic current is carried almost entirely by ferrous ions, which may be assigned a transport number of one. THERE has been increased evidence in recent years that the constitution of liquid-oxide systems (slags) is ionic.1-3 The principal studies designed to establish the structure of liquid slags have been by electrochemical methods', " and conductivity measurements1,6,7 which also have indicated the presence of semiconduction in several silicate systems1,4-0 and in pure iron oxide.' It is well known that many slag-forming metallic oxides have an ionic lattice type in the solid state, and their properties are determined to a large extent by the lattice defects and ion sizes. As Richardson8 as pointed out, the detailed models of liquid slags cannot be found on thermodynamic data only but "must rest on a proper foundation of compatible structural and thermodynamic knowledge, combined by statistical mechanics." A careful thermodynamic study of the iron-silicate slags has been carried out by Schuhmann with Ensio9 and with Michal.10 They obtained experimental data relating equilibrium CO2: CO ratios to slag composition and made thermodynamic calculations of the activities of FeO and SiO, and of the partial molal heats of solution of FeO and SiO2 in the slags. It was found that the activity-composition relationships deviate considerably from those to be expected from an ideal binary solution of FeO and SiO2. However, the partial molal heat of solution of FeO into the slags was estimated to be zero. Their experimental results were correlated with the constitution diagram for FeO-SiO2 of Bowen and Schairer,11 with the results of Darken and Gurry" on the Fe-O system, and with the work of Darken"' on the Fe-Si-O system. All these studies were found to be consistent with one another. The variation of the mechanism of conduction with composition in the liquid iron-oxide-silica system in the range from pure iron oxide to silica saturation (42 pct SiO2) in iron crucibles was reported in a preliminary note." The current efficiency, or conformance to Faraday's law, showed some ionic conductance at all compositions, the proportion increasing with the concentration of silica. The current-efficiency experiments since have been extended. Furthermore, transport-number measurements have been completed in silica-saturated iron silicates to determine the nature of the conducting ions. Experimental Current Efficiency in Liquid Iron Oxide and Iron Silicates using Iron Anodes: This study was carried out by passing direct current through slags in the range from pure iron oxide to iron oxide saturated with silica (42 pct silica), using pure iron rods as anodes and the iron container as the cathode. A copper coulometer was included in the circuit to indicate the quantity of current passed during electrolysis. Assuming that the cation involved is Fe-+, the theoretical quantity of iron lost from the anode according to Faraday's law may be calculated and when compared with the actual loss observed, gives an indication of the extent to which Faraday's law has been obeyed. It also gives an indication of the presence and extent of ionic conduction in the melt. Preparation of the Slags: About 100 g of chemically pure Fe,O, powder is placed in an iron pot which is heated by induction until the contents liquefy. In this way, FeO is produced according to the reaction Fe2O3 + Fe = 3 FeO. More Fe2O3 or SiO, powder is added and, when a sufficient quantity of molten slag is obtained, the induction unit is turned off, the pot withdrawn, and the molten slag poured on to an iron plate. Homogenization and Electrolysis of the Slag: Apparatus—After considerable development, the setup illustrated in Fig. 1 proved to be quite satisfactory. A is an Armco iron cylinder, 1 in. ID and 1/8 in. wall, consisting of three sections placed one on top of the other. The bottom section is a pot about 5 in. long with a small hole drilled in its bottom to allow withdrawal of gases during evacuation of the apparatus. The middle section is 6 in. long and consists of a pot which serves as the slag container, while the top section is a hollow-cylinder continuation of the slag-container pot. The height of this latter section is about 5 in., giving an overall length of approximately 16 in. The iron cylinder is constructed in this way for ease of fabrication, the individual sections becoming welded together after the

Jan 1, 1955

By M. J. Sinnott, H. B. Probst

AN extensive survey of the factors which affect austenite grain growth has already been made.' These factors are temperature, time at temperature, rate of heating, initial grain size, hot-working, alloy content, ofheating,initialand rate of cooling from the liquidus-solidus temperature. In the present work, a vacuum-melted temperature.electrolytic iron was used and the variables studies were temperature, time at temperature, and prior ferrite grain size. Other factors were maintained constant. The iron used in this study was vacuum-melted electrolytic iron of nominal composition of impurities of 0.07 wt pct. It was supplied as a ½ in. round cold-drawn bar. This iron was tested in three conditions: as-received, annealed 6 hr at 1200°F, and annealed 6 hr at 1600°F. Samples were ? in. disks cut from the bar. The prior anneals were carried out in vacuum and the isothermal treatments were carried out in vacuum-sealed Vycor tubing. The thermal etch technique was employed to determine the austenite grain size. Prior to sealing the test specimens, one surface of the sample was polished metallographically. This surface, after heating, was examined to determine the austenite grain size, since the austenite boundaries are revealed by thermal etching. This is essentially the only technique available for measuring the austenite grain size of low carbon steels or pure irons without altering the composition. It has been shown to yield results that are in agreement with other methods used for determining austenite grain sizes.' The specimen size was quite large compared to the grain size measured, so inhibition of growth due to size effects is probably negligible. After vacuum sealing, each sample was placed into a furnace at temperature and at the completion of the run was quenched into a mercury bath. The growth temperatures used were 1700°, 1800°, 1900°, and 2000°F controlled to -~10"F. Growth times were varied from 10 to 240 hr. The long times were used in order to eliminate the nucleation and growth effects occurring during the initial transformation. Time was measured from the introduction of the capsule into the hot furnace to the time of quench. Grain-size measurements were made with the use of a grain-size eyepiece of a microscope. By determining the number of grains per square millimeter at X100 and taking the square root of the reciprocal of this number, the average linear dimension of the grains was determined. Figs. 1 and 2 are plots of these data as a function of time and temperature for the various conditions investigated. The variation of D, the linear dimension of the grains, was assumed to follow the equation3 D = A tn. The curves of Fig. 1 were obtained from the data by the use of the least-squares method of analysis. Fig. 1 is for the growth of the as-received stock and Fig. 2 is for growth after prior treatments. Differentiating the foregoing equation gives an expression for the rate of growth dD/dt = G = nAtn-1 = nD/t. Both D and G as functions of t are given in Table I. It should be noted that G is a function of time; the growth rate is rapid at early stages and decreases with increasing time. Since increasing temperature increases the growth rate, it has been common practice to use the empirical relationship G = Go e-Q/RT to relate temperature to growth rate. The growth rate customarily has been taken at constant values of D on the basis that the rate of growth is related to the boundary surface tension and this is measured by the curvature of the boundary. At constant D values, the growth rate is a function of time and temperature. The growth rate can be related however to temperature at constant time, and this has the advantage that under these conditions the growth rate is a function only of temperature. Obviously the Q values, activation energies, obtained for each assumption will not be the same and the question of which is the more correct is a moot one, since the assumed exponential relationship in either case has no particular theoretical significance. By plotting G, at constant grain size, vs 1/T, the activation energy over the temperature range of 1800" to 2000°F is found to vary from 30,000 cal per mol at the smaller grain sizes to 50,000 cal per mol at the larger grain sizes. The 1700°F data do not correlate with the data at higher temperatures. The activation energies for the 1200" and 1600°F prior annealed materials were calculated as 50,000 and 62,000 cal per mol, respectively, using the reciprocal time to a given grain size as a measure of the growth rate. Plotting G, at constant times, vs 1/T yields an activation energy of 12,300 cal per mol for the tem-

Jan 1, 1956

By John F. Elliott, John R. Rawling

The rate of reduction of silica to silicon by carbon at 1550° to 1700°C in iron blast-furnace type slag-metal systems has been investigated. In the tower portion of the temperature range oxygen transport in the metal boundary layer at the slag-tal interface is probably rate limiting. A second step, which apparently involves a chemical process in the slag at the slag-metal interface, appears to be rate limiting when the oxygen-transport limitation is avoided. Above 1650°C rate control of the reduction by carbon probably is mixed between the two steps. INVESTIGATIONS1.2 into the equilibrium distribution of silicon between graphite-saturated slags and metals typical of iron blast-furnace practice show that, under the experimental conditions specified, the reduction of silica to silicon is relatively slow compared with the rates of other slag-metal reactions under similar conditions. For this reason, the reduction of silica in blast-furnace slag-metal systems was considered to be an interesting subject for further study. Investigations of the kinetics of the reaction3-5 suggest that several possible steps may be rate controlling, and that the rate-controlling step depends not only on the physical state of the systems but also on the configuration of the apparatus. The main objects of the investigation reported here were to sug- gest plausible reaction paths for the reduction of silica under the experimental conditions chosen and to determine the step or steps which control the rate of reduction of silica. EXPERIMENTAL Two types of experiments involving the reduction of silica from the slag were carried out. In the first, the only reducing agent present was carbon (graphite), for which the over-all reaction is (SiO2) +2C(gr) —Si + 2Co(g) [l] The second type was a graphite-saturated ferro-silicon-iron concentration cell. In it silica in the slag could be reduced either by carbon according to Eq. [I], or by a reaction of electrochemical nature in which silicon was oxidized at the ferrosilicon-slag interface and silica was reduced at the slag-iron interface without the formation of CO. The two types of experiment are described below. Reduction of Silica with Carbon as the Only Available Reducing Agent. The reduction of silica was accomplished by allowing a liquid lime-alumina-silica slag and graphite-saturated iron to react in an induction-heated graphite crucible. The crucible was 2.25 in. diameter and 5 in. deep; it was fitted with a graphite stirrer which penetrated through the slag and into the metal, Fig. 1. The slag and metal charges weighed 350 g each. Pure carbon monoxide at a pressure of 1 atm was maintained above the melt by passing the purified gas through the crucible at a rate of 0.5 liter per min. The gas did not stir either the slag or metal. Temperature measurements were made by sighting an optical pyrometer down the hollow stirrer rod into a 1/4-in. hole drilled in the stirrer blade. The crucible temperature was maintained within *15"C of the required value by manual control of the power supply to the

Jan 1, 1965

By Robert J. Hite, Samuel S. Adams

Potash, the generic term for a variety of potassium-bearing minerals, ores, and refined products (Table 1), owes its importance as an industrial mineral to the potassium requirement of growing plants. The term potash originally referred to potassium carbonate produced by the leaching of wood ashes. This process, for which the first US patent was issued in 1790, was the basis for the largest United States chemical industry in the early nineteenth century. The agricultural use of potash soon eclipsed the chemical applications following the German discovery in 1840 that potassium is essential to plant growth. The initial discoveries of large deposits of soluble potassium minerals, essential for agriculture applications, were made in 1857 in Germany and in 1914 in the United States. More than 90% of the 27.5 Mt K20 produced in the world in 1980 (Searls, 1981) was derived from marine evaporite deposits and approximately 90% was used in fertilizers. The potassium content of an ore, mineral, or product is customarily expressed as % K20, a unit of measure which is neither a natural nor synthetic compound of potassium (1.0% K is equivalent to 1.2046% K2O). Geology Potassium, the seventh most abundant element in the earth's crust, is present in silicate minerals in igneous, sedimentary and metamorphic rocks. Potassium is also a major constituent of many surface and subsurface brines (Table 2). Economic potash deposits are essentially restricted, however, to widespread, thick accumulations of marine chloride evaporite deposits. These deposits yield high grade, large tonnage ore bodies, many of which are amenable to low cost mining and beneficiation. The products from these deposits are, moreover, ideal for use in fertilizer because of the high relative solubility of the potassium chloride and sulfate evaporite minerals. World potash production and reserves for such deposits so vastly overshadow other sources of potassium that the following discussion will be limited largely to potash deposits in marine evaporites with brief reference to certain potash-rich brines. Approximately 85% of current domestic production is from bedded salt deposits and much of the balance is from brines. Marine evaporite deposits are accumulations of salt minerals deposited in structural sedimentary basins through the evaporation of seawater or mixtures of seawater and other brines. The salt minerals are precipitated in assemblages and sequences of assemblages as determined by the compositions of the brines and the solubility relations in the salt systems (D'Ans, 1933). The evaporation of seawater normally yields carbonate minerals as the first precipitates (Table 3). Further evaporation and concentration of the brine leads to the precipitation, in succession, of sulfate, chloride, and supersaline mineral assemblages including the salts of potassium and magnesium. The common minerals, ores, and products of potassium deposits are listed in Table 1. Many potash deposits contain accessory evaporite minerals together with a variety of detrital and authigenic silicates (Braitsch, 1971). The structural basins within which marine evaporites occur are of two main types: (a) cratonic basins formed by broad epirogenic movements (for example, the Michigan Basin of the midwestern United States and the Permian Zechstein Basin of eastern Europe), and (b) grabens, commonly related to continental

Jan 1, 1983

By Aloys IL. Wollrab

The conditions that govern the selection of a suitable type of detachable bit for the small, isolated mine, for rock work and tunnel contracting and for the large mine are quite dissimilar, therefore intelligent recommendation of a particular make of detachable bit must involve consideration of many factors. Small, isolated mines may find advantageous a detachable bit that a larger mine cannot afford to use, because of more efficient conventional steel sharpening and steel-distribution practice, but a small mine may not be able to adopt the practice of large mines because of necessary capital expenditures for equipment for detachable-bit sharpening and . shanking. The perfect detachable bit, suitable for all conditions, has not yet been developed. Conventional Drill Bit in Use That drilling speed increases as the bit gauge decreases is well known, but since small-hole drilling is the exception rather than the rule the rate of such increase is probably not so generally recognized. Tests carried out by Holman Brothers Limited1 with 7/8-in. steel show that when bit sizes are reduced from I½ in., I3/8 in., and I3/16 in-; to I3/8 in., I1/4 in.., and I1/8 in., respectively, the volume of the hole is I 5 per cent less and the drilling speed 49 per cent higher. Recent tests by the United States Bureau of Mines2,3 in hard, uniform basalt showed that a reduction in average gauge from 2.077 to I,826 in., a difference of o.25I in., gave an increased drilling speed of 65 per cent. The limits to which a drill hole may be extended depend upon the loss in gauge. Since the conventional bit with 5° and 14° clearances did not possess sufficient reaming edge to permit the smaller gauge changes that were required for small-hole drilling, experiments were made in bit construction with a view to correcting this deficiency. This resulted in the adoption of the full reaming cross bit (having full Carr charac1erist.i~~) by some mines4 In order to drill holes having a minimum taper from the collar to the bottom of the hole, full reaming center-hole cross bits with 90° cutting angles, 5° and 14° wing tapers, forged on 7/8-in. quarter-octagon drill rods, are used in the conventional drill-steel practice at Hollinger. In the steel shop close attention is given to the condition of the dies and dollies, which, combined with a rigid inspection of the finished bit, ensures as nearly a perfect bit as call be forged economically. Shop practices and costs have been discussed in earlier paper.5,6 The method by which the radii for the special dies used for forging bits of different gauge diameter are obtained so that the points and reaming edges cut circles of the same diameter has been discussed by Hibbert. Requiremnts for Detachable. Bit for Hollinger Under these it it was appar- ent that it would be difficult to introduce a detachable bit that could successfully compete with the conventional bit already in

Jan 1, 1943

By Aloys IL. Wollrab

The conditions that govern the selection of a suitable type of detachable bit for the small, isolated mine, for rock work and tunnel contracting and for the large mine are quite dissimilar, therefore intelligent recommendation of a particular make of detachable bit must involve consideration of many factors. Small, isolated mines may find advantageous a detachable bit that a larger mine cannot afford to use, because of more efficient conventional steel sharpening and steel-distribution practice, but a small mine may not be able to adopt the practice of large mines because of necessary capital expenditures for equipment for detachable-bit sharpening and . shanking. The perfect detachable bit, suitable for all conditions, has not yet been developed. Conventional Drill Bit in Use That drilling speed increases as the bit gauge decreases is well known, but since small-hole drilling is the exception rather than the rule the rate of such increase is probably not so generally recognized. Tests carried out by Holman Brothers Limited1 with 7/8-in. steel show that when bit sizes are reduced from I½ in., I3/8 in., and I3/16 in-; to I3/8 in., I1/4 in.., and I1/8 in., respectively, the volume of the hole is I 5 per cent less and the drilling speed 49 per cent higher. Recent tests by the United States Bureau of Mines2,3 in hard, uniform basalt showed that a reduction in average gauge from 2.077 to I,826 in., a difference of o.25I in., gave an increased drilling speed of 65 per cent. The limits to which a drill hole may be extended depend upon the loss in gauge. Since the conventional bit with 5° and 14° clearances did not possess sufficient reaming edge to permit the smaller gauge changes that were required for small-hole drilling, experiments were made in bit construction with a view to correcting this deficiency. This resulted in the adoption of the full reaming cross bit (having full Carr charac1erist.i~~) by some mines4 In order to drill holes having a minimum taper from the collar to the bottom of the hole, full reaming center-hole cross bits with 90° cutting angles, 5° and 14° wing tapers, forged on 7/8-in. quarter-octagon drill rods, are used in the conventional drill-steel practice at Hollinger. In the steel shop close attention is given to the condition of the dies and dollies, which, combined with a rigid inspection of the finished bit, ensures as nearly a perfect bit as call be forged economically. Shop practices and costs have been discussed in earlier paper.5,6 The method by which the radii for the special dies used for forging bits of different gauge diameter are obtained so that the points and reaming edges cut circles of the same diameter has been discussed by Hibbert. Requiremnts for Detachable. Bit for Hollinger Under these it it was appar- ent that it would be difficult to introduce a detachable bit that could successfully compete with the conventional bit already in

Jan 1, 1943

By F. F. Aplan, P. H. de Bruyn

The adsorption density of hexyl mercaptan was measured at the gold-solution and the gold-vapor interfaces. This collector is strongly adsorbed at low concentrations, a monomolecular layer being formed at the gold-solution interface at concentrations as low as 2 x 10'6 moles per liter. A maximum contact angle of 83 ± 3° is observed. From a thermodynamic analysis of the experimental data the changes in surface tension at the gold-gas and gold-solution interface are calculated. The data also suggest that the adsorption density of mercaptan at the gold-gas interface exceeds that at the gold-solution interface. In the equilibrium state, a simple flotation system consists of three phases, the solid to be floated, air, and an aqueous solution in stable contact along a line. During the process leading to this final state, a solid-gas interface is created at the expense of a portion of the liquid-gas and solid-liquid interfaces. This change of state is achieved by addition of a collector and, if necessary, suitable modifying agents to the system. By a combined application of the Gibbs Adsorption and the Young Equations, de Bruyn, Overbeek and Schuhmannl were able to show theoretically that the equilibrium distribution of the collector at all three interfaces determines the magnitude of the contact angle. Their analysis led them to conclude that the equilibrium adsorption density of the collector at the solid-gas interface exceeds its density at the solid- liquid interface. This paper succeeded in focussing attention on the neglected role of the solid-gas interface in flotation. In recent years the application of radiotracer, infrared, electrochemical and electro-kinetic techniques to studies of the solid-liquid interface2-5 enhanced our understanding of adsorption processes at this interface. Except for the measurement of contact angles, the solid-gas interface received no attention in fundamental flotation studies. In an attempt to apply the analysis of de Bruyn, Overbeek and Schuhmann to a simple flotation system, an investigation of the adsorption of hexyl mercaptan onto gold was undertaken. Gold was chosen as the solid phase in order to keep the number of dissolved chemical species in the solution phase to a minimum. Hexyl mercaptan (1 - hexanethiol) was selected as collector because its relatively high vapor pressure at room temperature makes it possible to obtain adsorption measurements at the solid-gas interface. This flotation system consists, therefore, of a pure solid phase (gold), an aqueous solution of a weakly dissociated collector (1 -hexanethiol), and a gaseous phase, nitrogen saturated with respect to both water vapor and mercaptan vapor. EXPERIMENTAL MATERIALS AND METHODS Materials: Liquid 1-hexanethiol (C6H13SH) was obtained from Distillation Products Industries and was further purified by double distillation. The purity of the final product was established by boiling point and refractive index measurements. For the adsorption studies from aqueous solution, the radiotracer element, sulfur-35, (half life 87.1 days, 0.169 Mev beta ray) was synthesized into the mercaptan by Tracerlab Inc., Boston, Mass. A close boiling fraction of the synthesized compound was used in the adsorption studies. The specific activity of the radioactive compound was 10 millicuries per gram.

Jan 1, 1963

By K. A. Johnson, F. H. Ellinger, C. C. Land

The Pu-In phase diagram has been determined by thevmal, filtvation, micrographic, and X-ray diffraction methods. This alloy system is characterized by 1) limited solubility of indium (-2 at. pet) in 6 and e plutonium, 2) one eutectic, and 3) fizte intermediate phases. Of the latter, PuIn and PuIn3 melt con-gruently, and Pu31n, Pu31n5, and the high-temperatuve 7 solid solution are formed peritectically. The n phase decomposes eutectoidally into Pu3In and PuIn at 865°C. Although the 6 phase can readily be retained to room temperature, it is not thermo-dynamically stable below 300°C. The Pu-In system has been investigated at Los Alamos as part of a study of the alloys of plutonium with the group 111-B elements. Constitutional studies of the Pu-A1 and Pu-Ga systems have been reported earlier.'9' To date, published information on the constitution of Pu-In alloys covers only the identification of the intermediate phases Pu3In and PuIn3.3,4 EXPERIMENTAL The alloys were prepared from five different lots of plutonium and three different lots of indium. The principal impurities in the plutonium differed from lot to lot within the following limits (in ppm): iron, 30 to 80; nickel, 30 to 60; aluminum, 15 to 30; silicon, 20 to 145: thorium, 50 to 300; carbon, 75 to 335; and oxygen, 20 to 135. Spectroanalysis of the indium showed that two of the lots were 99.9 wt pct pure, and the third was 99.98 wt pct pure. The alloys, in the form of about 5-g buttons, were prepared by arc melting in conventional equipment. The components for each alloy were weighed to the nearest 0.1 mg. In most instances the weight losses during melting were negligible; therefore confirmatory chemical analyses were usually not made. A few results are given in Table I. Density measurements of the arc-cast buttons were made by the liquid displacement of bromoben-zene. Heat treating was done in muffle furnaces controlled to +2°C. The alloy buttons were wrapped in tantalum foil before being enclosed in evacuated clear silica capsules. As a precaution against breakage, each capsule was in turn placed in a silica tube closed with a refractory wool plug prior to being charged into the furnace. For a moderately fast quench of the alloys, the outer protection tubes containing the capsules were plunged into cold water. Differential thermal analyses (DTA) in racuo were performed at heating and cooling rates of about 1.5°C per min. Tantalum crucibles having inverted thermocouple wells were used for most of the analyses. It was found micrographically, however, that the liquid alloys containing more than about 35 at. pct In reacted with the tantalum, resulting in contamination of the surface of the alloy. A search for a more satisfactory crucible material was not successful: tungsten and yttria behaved comparably to tantalum; thoria, vitrified magnesia, and vitrified alumina severely contaminated the alloys. So as to minimize the contamination by the crucible mater-

Jan 1, 1965

By R. M. Brick, J. T. Richards

Tests have been conducted to determine the mechanical properties of several beryllium copper alloys down to liquid air temperatures. The materials investigated include beryllium copper, beryl-lium-cobalt-copper, and beryllium-zinc-copper in the wrought and cast conditions. As a means of evaluation, the influence of cold work and age hardening treatment upon subzero behavior has been observed. The effects of temperature upon both elastic and plastic deformation are also considered. THE low temperature mechanical properties of beryllium copper are of current interest in view of the increasing number of subzero applications. At extremely low temperatures, beryllium copper components are employed in temperature control and gas liquefaction equipment. At more moderate temperatures, such as those encountered in arctic regions, these alloys find use in a wide range of civilian and military applications. Although several previous subzero investigations have included beryllium copper,'-' none have been complete with respect to test temperatures or materials employed. As indicated in Table I, the alloy: used by Colbeck and MacGillivray,1 Walle,2 and Kostenets' were nonstandard and were not representative of present commercial practice. In addition, Kostenets4 did not test age hardened specimens, while the temperature in the other investigations", "-' were not carried below —100°F. These tests, however, indicate that beryllium copper offers interesting possibilities in subzero atmospheres, since the increase in strength with decreasing temperature is not accompanied by a reduction in ductility or impact resistance. As a means of checking and extending this earlier work at subzero temperatures, an investigation was undertaken at the University of Pennsylvania. In addition to testing the standard 2 pct beryllium copper, other alloys were also considered in wrought and cast forms. Charpy impact and tension tests were included with particular emphasis on the elastic characteristics, since beryllium copper is frequently selected for its spring qualities. Nominal test temperatures were +80°, —75", —200°, and —300°F. Test Materials Wrought beryllium copper, beryllium-cobalt-copper, and beryllium-zinc-copper specimens were machined from 0.560 in. diameter rod. These alloys were tested in the solution treated, cold drawn, or age hardened conditions. In the case of solution treated beryllium copper, some specimens were aged (3 hr at 600°F) for maximum hardness and others were overaged (1 1/2 hr at 750°F) to determine the effect of heat treatment. The compositions and average room temperature properties of these wrought alloys are presented in Table 11. The casting alloy versions of beryllium copper and beryllium-cobalt-copper were prepared as sand-cast cylinders, roughly 3/4 in. diameter x 6 in. long. Test specimens were machined from these cylinders. Conditions tested included as cast as well as solution treated and age hardened. Table 111 lists compositional and room temperature property data for the cast alloys. Test Methods Tension tests were conducted on specimens having a 0.25 in. diameter reduced section over a 1 in. gage length. To insure axiality, specimens were loaded by means of hardened chains. The yield strength at 0.2 pct offset was obtained from autographically recorded stress-strain curves resulting from a spe-

Jan 1, 1955

By G. C. Kuczynski

Two particles in mutual contact form a system which is not in thermo-dynamical equilibrium, because its total surface free energy is not a minimum. If such a system is left for a certain period of time, the bonding of the two particles will take place in order to decrease the total surface area, even though the temperature is lower than the melting point. This phenomenon of bonding of two or more particles with the application of heat only and at temperatures below melting point of any component of the system will be called sintering, although the powder metallurgists use this term in a broader sense, including the presence of molten phase and pressure. It is the objective of this paper to study this process and the mechanisms involved in it. This problem is of utmost importance to powder metallurgy and powder ceramics, and its technological aspects have been studied for a good many years. However, the powder metallurgical operations are too complex and include too many superimposing mechanisms, and too many variables for a direct study. It was therefore advisable for the purposes of this study to reduce the variables to a minimum. In this work the radius of the interface formed during bonding in a simple system composed of a spherical particle and a large block of the same metal was studied as a function of time and temperature. It is believed that the mechanism involved in this simple process is fundamental to any sintering operations. Previous Work J. Frenkell was the first to make a serious attempt to develop a theory of sintering. He assumed that the process consists of a slow deformation of crystalline particles under the influence of surface tension which reduces to a viscous flow where the coefficient of viscosity n is related to the self-diffusion coefficient D by the following equation 1 _ D D6kT [1] where 6 is interatomic distance, k the Boltzman constant, and T the absolute temperature. This type of viscous flow of a crystalline substance is essentially different from the ordinary plastic flow. The latter is a specific propcrty of crystals and cannot take place in amorphous bodies. According to Frenkel this viscous type of flow is due to the diffusion of the holes or vacancies arising in the lattice. He was able to derive an equation relating the growth of the interface between two spherical crystalline particles or between a particle and a semi-infinite crystal (Fig 1) to time t at constant temperature. This relationship can be written as follows: x²— 3/2 a/nt [2] where x is the radius of the interface assumed to be circular, a the original radius of the sphere and a surface tension of the material. The other assump- x tions are that x is less than 0.3 and that during the period 1 the original radius, a, of the metallic particle did not change appreciably. A. J. Shaler and J. Wulff2 followed closely the ideas of Frenkel in their theory of sintering of a mass of metallic powder. Neither Frenkel nor Shaler has validated his theoretical speculations with conclusive experimental data. Two measurements reported by

Jan 1, 1950

By M. C. Flemings, P. J. Ahearn

Dendvite morphology of unidirectionally solidified Sn-12 pct Bi alloy was determined with the aid of X-ray and macroetch techniques. Columnar growth direction (growth direction of primary arms) in this alloy is [110]; secondary arms grow in the [lii], [111), and [112] directions. Interstices between [112] dendrite arms fill in during early stages of solidification so that well-defined (110) planes are seen in the final structure (parallel to the heat-flozo direction). Similarly, interslices betweex the [111] secondary arrlls fill in to form (112) planes, and interstices between [1111 ] arms fill in to form (112) planes. DENDRITE morphology in alloys is conveniently studied in unidirectionally solidified castings. In this type of solidification, heat is extracted from a single chill surface of the casting while other surfaces are insulated. Solidification progresses from the chill and results in cast grains that are columnar with the long axis of the grain perpendicular to the chill. Dendrite morphology is conveniently studied by examination of etched surfaces parallel and perpendicular to the chill, as previously described.'" Experimental studies on the growth direction for tin are in general agreement. The major growth direction is [110]:-' although this is altered somewhat by supercooling. In one study, tin dendrites pulled from a supercooled melt had a growth orientation 12 deg away from the [110] direction toward the [002] direction.' This orientation could be changed back to the [110] or close to the [110] direction by changing the tempera- ture gradient in the melt. In a study using autoradio-graphic techniques, (111) directions were shown to be directions of preferred growth in addition to the [110) direction.7 PROCEDURE The samples employed in this study were cut from 12 pct Bi-88 pct Sn castings, 1.5 in. in diam and 3.5 in. tall. The casting procedure consisted of heating the charge to 390°C and then pouring the molten alloy directly into a gypsum sleeve mounted on a massive copper chill. Specimens were cut from the ingot, mounted, polished, and etched with Taffs reagent [FeC13 .6H2O, 2 g; HC1, 5 cu cm;H20, 30 cu cm; CzHaOH (95 pct), 60 cu cm].' The dendritic pattern was clearly visible after etching. Photomicrographs at about 8 and 35 times were taken on surfaces parallel and perpendicular to the chill. Laue back-reflection patterns were obtained from three different columnar grains in a singIe polished face 2 in. from the chill. The cut face was polished and positioned in the beam of a Laue camera, so that diffraction occurred from a single dendritic grain. The resulting diffraction pattern was interpreted to determine crystal log raphic orientation in relation to the heat-flow direction and in relation to microstruc-ture of the given grain. RESULTS Fig. 1 shows a horizontal and vertical section of the columnar structure, at low magnification. Light regions are rich in tin, and darker regions tin-poor; the primary phase is tin-rich a phase. The two sections shown were taken orthogonally from the same metallographic specimen. It is readily seen from Fig. 1 that the dendrites have

Jan 1, 1968

By W. Vickers

Single-point rotating cantilever fatigue tests have been carried out at 550" to 650°C on beryllium produced by a variety of fabrication routes. All the specimens gave similar plots of stress against number of cycles to failure but failure occurred at a lower stress range in the hot-pressed material than in the extruded material. A discontinuity or "kink" appears to exist in the curves and this is considered. A true endurance limit was not evident up to 10 cycles. When Brush hot-pressed warm-extruded beryllium was tested at 600oC a relationship where Nf = number of cycles to failure, ?ep = plastic strain range, and c = constant, was shown to be applicable for values of ?ep > 6.3 x 10-4. Further for this moterial and temperature and for frequencies between 150 and 4500 cycles per min, the variation of number of cycles to failure with frequency obeyed the expression N = Af0.44 where N =number of cycles to failure, f = frequency, and A = constant. Examination of the fracture surfaces indicated that they were generally intergranular and in all cases the higher the stress the more irregular was the fracture. Microexamination has shown that grain boundary cavities and fine intergranular cracks were associated with the fractures. REVERSING or cyclic stresses set up in fuel elements can lead to failure by fatigue. Fatigue stresses may be developed by instability of the fuel element in the coolant flow leading to rattling against the channel wall or fin vibration. Thermal cycling also sets up reversing stresses due to differential expansion of fuel and can. Fatigue resistance is of some importance therefore in the evaluation of canning materials. At the time the work described in this paper was initiated, beryllium was being considered for the can and endcaps of an advanced gas-cooled reactor fuel element. With this in mind, beryllium obtained from different manufacturing routes was tested on single-point rotating cantilever fatigue machines at temperatures the same as those envisaged in the reactor to obtain appropriate fatigue data. The results obtained indicated a discontinuity in the S-N curves coinciding with the yield stress in the specimens. Although in some cases the data is insufficient to warrant a detailed quantitative analysis, a qualitative analysis of this effect was thought to be justified. 1) EXPERIMENTAL DETAILS The materials used are given in Table I together with the production route and available analyses. The specimen shape is shown in Fig. 1. The fatigue specimens were machined slightly oversize, after which they were given a stress-relieving anneal of 1 hr at '750° C in vacuum. This was followed by an etch in sulfuric-phosphoric-chromic acid mixture down to the finished dimensions given in Fig. 1. Etching served to remove the interference colored oxide film formed on the surface during annealing and very small recrystallized surface grains too. The specimen was mounted in the grips of a cantilever machine and rotated inside a furnace controlled at the testing temperature. The specimen was loaded in increments as the speed was increased until the required load was applied at 5000 cycles per min. A revolution counter was used to record the total number of cycles.

Jan 1, 1964

By C. C. Clark, J. S. Iwanski

The purpose of this investigation was to study mi-crostructural changes that take place in a commercial nickel-chromium-iron alloy, such as Incoloy "901," over long periods of time at temperatures up to 13 50°F and to correlate such changes with creep-rupture properties. of the alloy. In the course of the investigation, some microstructural changes were observed which correspond to microstructural alterations found in previous studies of Inconel "X." Microstructural phases have been identified in both alloys with the aid of electron and X-ray diffraction and an electron probe microanalyzer. The materials used in this investigation were from commercial heats of the following chemical composition: Pct Cr Pct Ni Pct Mo Pct Fe Pct Cb Incoloy "901" 12.51 43.67 5.72 Bal. -Inconel "X" 14.61 73.44 - 6.61 1.02 Pct A1 Pct Ti Pct Mn Pct Si Pct C Incoloy "901" 0.10 2.46 0.46 0.24 0.05 Inconel "X" 0.70 2.43 0.51 0.36 0.04 Long-term creep-rupture tests were conducted on Incoloy "901" at temperatures of 1000°, 1200°1 and 1350°F. A summary of these results is shown in Table I along with the results of a long-term creep-rupture test conducted on Inconel "X" at 1500°F. The heat treatments given the specimens are also shown in Table I. When the creep-rupture results on Incoloy "901" are compared with shorter-tertn data, there is no evidence of any undue deterioration of the creep-rupture strength with time, nor is the elongation decreased more than would be expected from the influence of time alone. INCOLOY "901" PHASE IDENTIFICATION Microscopic examination of the Incoloy "901" specimens reveals a dark etching grain boundary constituent in the specimen which was under test for about 11,500 hr at 1000°F. This grain boundary constituent was seen to increase in size as the test temperature was increased to 1200" and 1350°F, Figs. 1, 2, and 3. Simultaneously, an acicular structure of definite crystallographic orientation appears within the grains of the 1350°F specimen, Fig. 3. Under examination with the electron microscope, a fine precipitate is observed in the 1200 °F specimen. Fig. 4. It becomes considerably larger in the 2850-hr 1350°F specimen, Fig. 5. In a few areas the precipitated particles have been replaced by, or transformed to, small needles or platelets. After 7380 hr at 1350°F, Figs. 3 and 6, the needles are much larger and have replaced nearly all of the fine precipitate. X-ray diffraction studies detected the presence of hexagonal Laves phase and hexagonal n phase (Ni,Ti) in the 1350°F specimens, Table 11. Only the Laves phase was detected by X-ray diffraction in the 1200°F specimen and none was detected in the 1000°F specimen. In this latter specimen, however, the small quantity of precipitate in the grain boundaries (presumed to be Laves phase) precludes its detection by X-ray diffraction. Composition of the hexagonal Laves phase is not yet known, although its diffraction

Jan 1, 1960

By Irving Cadoff, Richard Nolder

An analysis oj a series of samples of single -crystal silicon grown on sapphire shows that ,four distinct orientation relations exist. There are at least thirteen crystallographic planes which serve as substrates ,for epitaxial growth The model which assumes that silicon substitutes for aluminium and bonds with the oxygen atoms of the sapphire to form the first later for subsequent growth can account for the epitaxial geometry in all four cases. Multiplici-ties 01 specific orientations are found which are explained by the symmetry of both the sapphire and silicon crystal structures. It was reported in the previous paper' that single-crystal silicon films can be deposited on single-crystal a A1,03 (sapphire) with a wide variety of orientations. The silicon films, however, were found to deposit in only four different orientation relationships with respect to the sapphire substrate. The X-ray data have been analyzed to determine the plane and direction of atomic fit and an atomic model to account for the epitaxial relationships at the silicon-sapphire interface has been developed. These results are described in the present paper. EXPERIMENTAL The Laue X-ray data described in the previous paper were reduced to stereographic projections in a standard manner. These data were supplemented with X-ray reflection data obtained with -& E and A Full-Circle Goniometer (Electronics and Alloys, Inc.) mounted on a Phillips diffractometer unit. The silicon films were thin enough to result in characteristic reflections from the substrate as well as the silicon. The superimposed stereographic projections were analyzed to determine the orientation relationships. Ambiguities were resolved by referring to constructed models of various lattice planes for both silicon and sapphire. These lattice models were also used to develop the model for atom fit at the interface. DATA AND ANALYSIS 1) Crystal Structures. The crystallography of silico-n, which is of the diamond cubic class with a. = 5.4~, is straightforward. The sapphire structure is more complex and generally difficult to represent in pictorial form. It is of the rhombohedra1 class but usually referred to hexagonal axes. The transformation of indices between these two systems can lead to ambiguities which will have bearing on the analysis presented herein. Therefore, the basis used in this paper is described in the appendix. Referred to the hexagonal system, the parameters of sapphire are co = 12.95.&, a, = 4.75~, c/a = 2.73. All parameters are for room temperature. Figs. 1 and 2 illustrate schematically the hexagonal unit cell model of sapphire used for this analysis. The oxygen atoms are assumed to occupy positions in an idealized hexagonal array on basal planes. Their actual positions are in a slightly distorted hexagonal array. The aluminum-atom positions are scaled to their actual positions in the lattice with respect to the basal layers of oxygen atoms. It was found that an idealized model where the aluminum atoms are assumed to lie exactly at the octahedral interstices of the oxygen lattice, similar to that used by ~ronberg,' was not adequate for this study.

Jan 1, 1965

By George G. Binder Jr., James W. Lacey, Arthur L. Draper

An experimental investigation of miscible fluid displacement has been made in linear porous media under highly adverse mobility ratio conditions. Various refined oils were displaced at field rates by liquid propane in both horizontal and vertical models 9 to 36 ft in length. In horizontal tests, mixed zones or transition zones form between the two liquids early in the displace-lents. Initially, the zones grow rapidly. III 2-in. diameter models, the mixed regions become nearly stable zones from 6- to 20-ft long. From then on these quasi-stable zones apparently grow only by molecular diffusion. The lenghts of the quasi-stable zones appear to be almost independent of the core material in which displacement;; are made and increase with increasing rates of injection and oil/solvent viscosity ratios. The lengths of the quasi-stable zones. measured in 2-in. diameter models at viscosity ratios and injection rates anticipated in the field indicate that essentially piston-like displacements of oil by solvent would occur. However, the mixed zone lengths increase markedly as the model diameter increases. In vertical displacements controlled by gravity drainage, only short trans-sition zones form. The entire lenghts of these zones can be accounted for by molecular diffusion. Therefore, in reservoirs having characteristics allowing a high degree of gravity drainage, nearly complete oil recovery should be attainable by miscible fluid displacement. INTRODUCTION The oil industry is faced with an ever increasing cost for finding new oil reservoirs. This, coupled with the fact that conventional methods of oil recovery usually leave from 1 to 3 bbl of oil in the ground for every barrel produced, has aroused considerable interest in developing more efficient methods. An integral part of the mechanism of many of these new methods of recovery is a miscible fluid displacement in which oil is displaced by a much less viscous materiai such as liquid propane. A numher of irlvestigators have explored the mechanics of miscible fluid displace-ment,'.2.1.'."." but in the experiments reported many of the important factors have been varied only over a limited range far removed from norma1 oilfield values. This paper presents the results of an experimental study of oil displacement by liquid propane at field rates from linear, natural-sandstone models of various sizes. Both horizontal and vertical flow tests were made. EXPERIMENTAL APPARATUS AND PROCEDURE Refined oils with viscosities varying over a wide range were displaced at several rates by liquid Propane from both horizontal and vertical flow systems. The behavior of the displacement was observed by propane-oil analyses of the effluent and, when possible, by differential pressure measurements along the cores. A schematic flow diagram of the apParatus used to conduct the experirents is shown in Fig. 1. The cores used in the tests were 9-ft lengths cut from natural consolidated sandstone and turned to the desired diameter. These were cast in steel tubing with a low melting point (160°F) alloy which expands on solidification. Flanges welded to the ends of the steel pipes permitted sealing the ends or butting one core to another. Pressure seals were maintained with O-rings. The cores were cleaned by flushing

By H. T. Clark

NO previous determinations of the deformation or recrystallization textures of titanium or of titanium-base alloys have been reported in the literature. The room-temperature structure of titanium is hexagonal close-packed with a c/a ratio less than 1.633. It would be expected, therefore, to have a rolling texture similar to that of other hexagonal close-packed metals, namely (0001) [1010]. Burgers and Jacobs1 have shown that zirconium, a metal isomorphous with titanium in its structure and similar in many of its properties, has such a texture with a scatter of the basal plane toward the transverse direction. This scatter is in the opposite direction from that found in magnesium by Bakarian2 but similar to that reported by Smigelskas and Barrett3 or beryllium. The rolling and annealing textures reported here for high-purity iodide titanium are significantly different from the . textures of any other hexagonal close-packed metal. All titanium used during this investigation was prepared by the iodode process." The annealed hardness of this material varied from 73 (material used for sample No. 2) to 97 Vickers hardness number. An estimate of the chemical composition of this grade of titanium has been reported by Finlay and Snyder.5 With one exception, shown in table I, the as-deposited titanium was cast into 10 to 20 g ingots in an electric arc furnace in purified argon before being rolled to sheet. The cast ingots were forged and ground until their cross-section was approximately rectangular, annealed 1 hr at 700°C in vacuum and cold rolled. Rolling was carried out in a two-high, 4 in. diam mill, using reductions no greater than 10 pct per pass. The direction of rolling was reversed after each pass, and, in order to avoid temperature effects, the sheet was allowed to cool after each pass. Unless the rolled sheet was sufficiently thin for X-ray penetration (about 0.004 in.), it was reduced to this thickness by pickling. Because of the possibility of introducing twinning or other deformation during grinding, no attempt was made to maintain uniform thickness of the sample during pickling by intermediate grinding or sanding operations. Those samples to be used for determining the annealed texture were recrystallized by vacuum annealing the cold-rolled sheet for 1 hr at 500°C. These thin samples were held between thick titanium sheets during annealing to prevent distortion. Table I outlines the rolling and annealing schedule of those samples for which photograms or texture patterns are shown. X-ray Techniques The usual techniques for determining textures were employed during this work. Molybdenum radiation was used for the transmission exposures and copper radiation for the glancing angle ones. Since titanium fluoresces under these conditions, it is necessary to employ a filter between the sample and the film. The Kß radiation filters are very satisfactory for this purpose. Sufficient grains having favorable orientation were present in both the cold-worked and in the cold-worked—500°C annealed samples to provide satisfactory patterns with the samples stationary. Because of the difficulties of comparing intensities of transmission photograms with those obtained

Jan 1, 1951

By D. G. Swarthout, J. W. Savage, R. W. Guard

The Nb-N constitution diagvam has been examined from 1100° to 1450°C at 1 atm N2 pressure. On the basis of- our work plus that of Brauer and coworkers the stable nitvide Phases are: a) a solid solutlion, basic niobium (bcc) with nitrogen contained interstitially; NbN,, x = <0.40; b) ß NhNx,x = 0.39 to 0.45; hexagonal (W2C type) (NbzN); a =3.058A,c = 4.961 + 0.001A c) y NbNx x = 0.75 to 0.80; tetragonal (distorted NaCl type) (Nb4N3); a = 4.386A,c = 4.332 + 0.001A; d) 6 NbN,, x = 0.88 to 0.91; cubic (NaCl type); a = 4.3885 + 0.0007A; e) E NbNx x = 0.92 to 1.00; hexagonal (Tip type); a = 2.958A, c = 11.272 * 0.0015A. In addition, a metastuble transition phase 6&apos; has been observed and occurs only during the transition 6 — E. 6&apos; NbN has these distinguishing parameters: NbNx,x = 0.96; hexagonal (anti-NiAs type); a = 2.94A, c = 5 .46A. The high-temperature phase fields in the system are governed by two reactions: a) 6 + Y + E, a entectoid reaction occurring at 1270" ± 20° C; b) o + N2 = E, a 2 012 1 reaction occurring at 1370" ± 20° C. As part of a study of the electronic low-temperature. properties of transition metal nitrides, a number of specimens of niobium nitride were prepared. Preliminary observations on these specimens showed several points of disagreement with data already in the literature. It was, therefore, decided to determine the constitution diagram for the Nb-N system between 1100" and 1450°C. The objective of this research was to define the temperature and composition regions of stability of the various phases and to explain the differences among previously proposed diagrams. Review of Previous Literature. The research on the Nb-N system to 1964 has been summarized by storms.&apos; Although he does not present a phase diagram, his review covers the research on the system thoroughly. One of the earliest works on NbN is that of Ascher-mann and coworkers2 who studied the superconductivity of the cubic 6 NbN. Subsequent work by Horn and ziegler,3 Cook, Zemansky, and Boorse,1 Rögener:5 Schroder6 and sellmaier7 has qualitatively confirmed the first results on superconductivity, although their methods of preparation differed considerably. The constitution diagrams proposed for the system by Brauer and Esselborn8 and Elliott9 are shown in Fig. l(a)and (b). The diagram in l(a) has been modified by more recent results in Brauer&apos;s laboratory (private communication). Although 6&apos; is shown on this diagram, Brauer has indicated that he now believes 6&apos; to be a metastable phase in the temperature range shown. The diagram of Elliott, Fig. l(b), is based primarily on the results of Elliott and Komjathy10 on ni-trided niobium strip or rod specimens examined by X-ray diffraction and metallography. It will be noted that these proposed diagrams are in conflict with respect to the temperature and composition ranges of

Jan 1, 1968

By John B. Campbell, George G. Binder, Loren H. Jenks

Conventional methods of producing crude oil generally leave in the depleted reservoir 1 to 3 bbl of oil for every barrel brought to the surface. This paper describes a field test which explores the possibility of using gas-driven liquid propane to improve oil recovery efficiency. Laboratory theoretical and experimental studies leading to the field test indicated that low residual oil values could be obtained using limited amounts of propane driven by gas. The field test involved (I) repressuring the reservoir to the vapor pressure of liquid propane, (2) injecting the liquid propane, and (3) injecting dry natural gas to drive the propane and oil to the producing wells. Considerable preliminary work, including new drilling, work-overs, and a pressure survey was necessary. During the test, oil production rates have averaged about nine times the final primary rates. The field average GOR is still below the pre-test value. Oil recovery to date is 112,000 STB. About one-third of the 143,-000 bbl of propane injected has been produced to date. Results of the C-2 block test are encouraging and larger, more definitive field projects ore indicated. INTRODUCTION The cost of finding new crude oil reservoirs continues to increase. Today the oil industry is drilling more and deeper wells and making fewer big discoveries. Nevertheless, the demand for oil and oil products increases each year. It is natural that oil companies, faced with this situation, concentrate on recovering more of the oil existing in our known crude oil reservoirs. There is room for much improvement. For every barrel of oil brought to the surface by present day methods of producing crude oil, generally 1 to 3 bbl are left behind in the depleted reservoirs. The "unrecoverable" oil in petroleum reservoirs is largely "trapped" by capillarity. Since flushing with a solvent is exceedingly effective in combatting oil loss due to capillarity, much effort in this direction has been made in recent years1,2,3,4,5. Liquefied petroleum gas (LPG) has been suggested as a relatively inexpensive. abundant, easily recoverable solvent for crude. Some operators have observed striking responses in oil recovery at production wells offsetting input wells in LPG storage reservoirs6,7,8. In spite of the low unit cost of LPG, however, it is uneconomic in general to inject a volume of LPG into a reservoir to remove a like volume of oil. A modification of solvent flushing in which a limited quantity of liquid propane is gas driven through a reservoir appears capable of recovering much more than 1 bbl of oil per barrel of propane injected. Also, most of the propane injected should be recoverable for sale or re-use. Since such a process could well have widespread and profitable application, The Carter Oil Co. is making an extensive evaluation of the technique&apos;s possibilities. Laboratory development of the gas-driven propane recovery technique was sufficiently encouraging to justify testing in the field. Since 1952, the Production and Research Departments of The Carter Oil Co. have cooperated in a field test in the C-2 Block leases of the

Jan 1, 1958